The effect of Nb or Ta substitution into the M1 phase of the MoV(Nb,Ta)TeO selective oxidation catalyst

We use aberration corrected high-angle annular dark field (HAADF) imaging to systematically study, atomic column by atomic column, the effects of substituting Nb or Ta into the M1 phase of the MoV(Nb,Ta)TeO propane (amm)oxidation catalyst.The HAADF results indicate that the x,y coordinates of the metal sites within the M1 framework are unaffected by the substitution of either Nb or Ta for Mo. The HAADF analysis of the Ta-substituted catalyst demonstrated that the Ta preferentially substitutes into the pentagonal bipyramidal site, and by analogy, we anticipate that Nb substitutes similarly. Compositional analysis of the entire framework suggests that Ta/Nb behaves as a director of V among the octahedra that link the pentagonal rings, and the variable V occupancy may be correlated with variations in catalytic activities and selectivities. Finally, HAADF imaging provided evidence of coexistence of Ta-rich and Ta-poor domains. Similar phase segregation behavior may be present in Nb-substituted specimens, but Would be very difficult to detect. (C) 2008 Elsevier B.V. All rights reserved.